CN108172523B - The forming method of core material and semiconductor package body and salient pole - Google Patents

The forming method of core material and semiconductor package body and salient pole Download PDF

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Publication number
CN108172523B
CN108172523B CN201711286173.4A CN201711286173A CN108172523B CN 108172523 B CN108172523 B CN 108172523B CN 201711286173 A CN201711286173 A CN 201711286173A CN 108172523 B CN108172523 B CN 108172523B
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solder
mass
core
core material
plating layer
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CN108172523A (en
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西野友朗
近藤茂喜
服部贵洋
川崎浩由
六本木贵弘
相马大辅
佐藤勇
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Senju Metal Industry Co Ltd
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Senju Metal Industry Co Ltd
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L24/00Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
    • H01L24/01Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L24/10Bump connectors ; Manufacturing methods related thereto
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
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    • H01L23/00Details of semiconductor or other solid state devices
    • H01L23/48Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor
    • H01L23/488Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor consisting of soldered or bonded constructions
    • H01L23/492Bases or plates or solder therefor
    • H01L23/4924Bases or plates or solder therefor characterised by the materials
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/10Electroplating with more than one layer of the same or of different metals
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B23MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23KSOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K1/00Soldering, e.g. brazing, or unsoldering
    • B23K1/0008Soldering, e.g. brazing, or unsoldering specially adapted for particular articles or work
    • B23K1/0016Brazing of electronic components
    • BPERFORMING OPERATIONS; TRANSPORTING
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    • B23KSOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/02Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape
    • B23K35/0222Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape for use in soldering, brazing
    • B23K35/0227Rods, wires
    • BPERFORMING OPERATIONS; TRANSPORTING
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    • B23KSOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/02Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape
    • B23K35/0222Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape for use in soldering, brazing
    • B23K35/0244Powders, particles or spheres; Preforms made therefrom
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    • B23KSOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/22Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
    • B23K35/24Selection of soldering or welding materials proper
    • B23K35/26Selection of soldering or welding materials proper with the principal constituent melting at less than 400 degrees C
    • BPERFORMING OPERATIONS; TRANSPORTING
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    • B23K35/00Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/22Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
    • B23K35/24Selection of soldering or welding materials proper
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    • B23K35/262Sn as the principal constituent
    • BPERFORMING OPERATIONS; TRANSPORTING
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    • B23KSOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/22Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
    • B23K35/24Selection of soldering or welding materials proper
    • B23K35/26Selection of soldering or welding materials proper with the principal constituent melting at less than 400 degrees C
    • B23K35/264Bi as the principal constituent
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    • H01L23/498Leads, i.e. metallisations or lead-frames on insulating substrates, e.g. chip carriers
    • H01L23/49811Additional leads joined to the metallisation on the insulating substrate, e.g. pins, bumps, wires, flat leads
    • H01L23/49816Spherical bumps on the substrate for external connection, e.g. ball grid arrays [BGA]
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    • H01L24/80Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected
    • H01L24/81Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a bump connector
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    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00Apparatus or processes for manufacturing printed circuits
    • H05K3/30Assembling printed circuits with electric components, e.g. with resistor
    • H05K3/32Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits
    • H05K3/34Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by soldering
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
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    • H01L2021/60007Attaching or detaching leads or other conductive members, to be used for carrying current to or from the device in operation involving a soldering or an alloying process
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Abstract

The forming method of core material and semiconductor package body and salient pole is provided.The core material is that will to be solder alloy comprising Sn and Bi (Sn-Bi) form core material obtained from plating film on the surface of core (12), its be the Bi in soft solder coating layer (16) with the concentration of prescribed limit than the core material being distributed in soft solder coating layer, be the core material with the concentration of Bi than being distributed in 91.7~106.7% prescribed limit in soft solder coating layer.Bi in soft solder coating layer is uniform.Therefore, will not there is a situation where as follows: inner circumferential side melts earlier than peripheral side, and it is poor to generate volume expansion in inner circumferential side and peripheral side, flies core material by bullet.It in addition, soft solder coating layer integrally substantially evenly melts, therefore will not be considered as the positional shift of the core material occurred because melting opportunity is irregular, therefore there is no inter-electrode short-circuits of attendant position offset etc. etc. to worry.

Description

Core material, semiconductor package and method for forming bump electrode
Technical Field
The present invention relates to a core material, a semiconductor package having a solder bump using the core material, and a method for forming a bump electrode.
Background
In recent years, with the development of small-sized information devices, electronic components mounted thereon have been rapidly miniaturized. In order to meet the narrowing of connection terminals and the reduction of mounting areas of electronic components due to the demand for miniaturization, Ball Grid Arrays (BGAs) in which electrodes are arranged on the back surface have been used.
An example of an electronic component to which BGA is applied is a semiconductor package. The semiconductor package is configured by sealing a semiconductor chip having an electrode with a resin. Solder bumps are formed on the electrodes of the semiconductor chip. The solder bumps are formed by bonding solder balls to electrodes of the semiconductor chip. A semiconductor package to which BGA is applied is mounted on a printed circuit board by bonding a solder bump melted by heating to a conductive pad of the printed circuit board. In recent years, in order to meet the demand for further high-density mounting, three-dimensional high-density mounting in which semiconductor packages are stacked in the height direction has also been developed.
When a semiconductor package mounted in a three-dimensional high density is a BGA and a solder ball is placed on an electrode of a semiconductor chip and subjected to a reflow process, the solder ball may be crushed by the weight of the semiconductor package. If such a situation occurs, there is a concern that: the solder is extruded from the electrodes, and the electrodes come into contact with each other, thereby causing short circuit between the electrodes.
In order to prevent such a short-circuit accident, a solder bump is proposed which is not crushed by its own weight as a solder ball or deformed when the solder is melted. Specifically, proposed are: a ball molded from metal or resin is used as a core, and a core material obtained by covering the core with solder is used as a solder bump.
Lead-free solder mainly composed of Sn is often used as the solder plating layer for the core. As a suitable example, Sn-based solder alloys containing Sn and Bi are cited (see patent documents 1 and 2).
The core material disclosed in patent document 1 is obtained as follows: a Cu ball is used as a metal, and a Sn-based solder alloy containing Sn and Bi is formed as a solder plating layer on the surface of the Cu ball serving as a core. Since the Sn-based solder alloy containing Bi has a low melting temperature of 130 to 140 ℃, it is used as a plating composition for the reason that thermal stress applied to a semiconductor package is small.
In patent document 1, plating is performed with a concentration gradient such that the Bi content in the solder plating layer is low on the inner side (inner circumferential side) and increases toward the outer side (outer circumferential side).
Patent document 2 also discloses, for the same reason as patent document 1: a solder bump is obtained by using a Cu ball as a core and forming a plating film on the core of a Sn-based solder alloy containing Sn and Bi. In patent document 2, plating is performed with a concentration gradient such that the Bi content in the solder plating layer is high on the inner side (inner circumferential side) and low on the outer side (outer circumferential side).
The technique of patent document 2 is a concentration gradient completely opposite to that of patent document 1. This is considered to be because the concentration control of patent document 2 is simpler than that of patent document 1 and is easier to manufacture.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2007-44718
Patent document 2: japanese patent No. 5367924
Disclosure of Invention
Problems to be solved by the invention
However, when a core material obtained by forming a plating film of a Sn-based solder alloy containing Sn and Bi on the surface of a Cu ball is placed on an electrode of a semiconductor chip and subjected to reflow soldering, the following problems occur in patent documents 1 and 2.
The technique disclosed in patent document 1 is a solder plating layer having such a concentration gradient that the Bi concentration is low on the inner peripheral side and high on the outer peripheral side, but in the case of such a concentration gradient (low on the inner side and high on the outer side), there is a concern that the timing of melting Bi may be slightly shifted between the inner peripheral side and the outer peripheral side.
If the melting timings are uneven, a portion where the core material has not been melted in the region on the inner peripheral surface side even if the outer surface of the core material has already been melted is mixed, and as a result, the core material is slightly displaced on the side where the core material has been melted. In high-density mounting with a narrow pitch, there is a fear that solder processing based on this positional deviation causes a fatal defect.
The concentration gradient of Bi of patent document 2 is opposite to that of patent document 1. In this case, a heat treatment by reflow soldering is also performed to connect the semiconductor packages. When the solder is melted by heating in a state where the Bi concentration in the solder plating layer is high on the inner periphery side and low on the outer periphery side as in patent document 2, the solder starts to melt from the Bi region on the inner periphery side because the Bi density on the inner periphery side is high. Even if the Bi region on the inner peripheral side melts, the Bi region on the outer peripheral side does not yet start melting, and therefore the Bi region on the inner peripheral side rapidly expands in volume.
A pressure difference occurs between the inner and outer circumferential sides (outside air) of Bi due to the difference in the velocity between the inner and outer circumferential sides due to the volume expansion, and when the outer circumferential side of Bi starts to melt, a Cu ball as a core may be ejected due to the pressure difference caused by the volume expansion of the inner circumferential side. This must be avoided.
In the Cu core ball having the solder plating layer made of the Sn-based solder alloy containing Sn and Bi, a problem occurs when Bi in the solder plating layer has a concentration gradient.
The present invention has been made in view of the above problems, and an object thereof is to provide a core material having a plated solder plating layer formed by plating a (Sn — Bi) solder alloy containing Sn and Bi on a core surface, wherein Bi contained in the solder plating layer is distributed in the solder plating layer at a concentration ratio in a predetermined range of 91.4 to 106.7%. In other words, the core material in which the Bi concentration ratio in the solder plating layer is made uniform (equalized) by making the Bi concentration ratio within a predetermined range, and the Bi concentration ratio within the entire region including the inner layer, the intermediate layer, and the outer layer in the solder plating layer is made within a predetermined range, and the semiconductor package using the core material are provided.
Wherein a core material in which Bi is uniformly distributed in a solder plating layer other than a base plating layer when the base plating layer such as Ni plating is applied between the core and the solder plating layer of an (Sn-Bi) based solder alloy is provided.
In addition, a semiconductor package having a bump using such a core material is provided.
The Bi concentration ratio (%) used in the present application means a ratio (%) of a measured Bi value (% by mass) to a target Bi content (% by mass) in a predetermined region of the solder plating layer, or a ratio (%) of an average value (% by mass) of the measured Bi value to the target Bi content (% by mass).
Since the Bi content in the predetermined region may be referred to as the Bi concentration in the predetermined region, the Bi concentration ratio (%) used in the present application refers to the ratio (%) between the measured Bi concentration and the target Bi concentration in the predetermined region of the solder plating layer and the ratio (%) between the average value of the measured Bi concentrations and the target Bi concentration.
In the measurement of the Bi content of the solder plating layer, the solder plating layer may be dissolved in the core material using an oxyacid or the like, and a known analysis method such as ICP-AES or ICP-MS may be used.
Means for solving the problems
To solve the above problems, the core material of the present invention described in item 1 has a solder plating layer of a (Sn-Bi) solder alloy containing Sn and Bi, which is formed by electroplating solder on a core surface,
the core is formed of a single metal of Cu, Ni, Ag, Bi, Pb, Al, Sn, Fe, Zn, In, Ge, Sb, Co, Mn, Au, Si, Pt, Cr, La, Mo, Nb, Pd, Ti, Zr, Mg, or an alloy, a metal oxide, or a mixed metal oxide of two or more of these metals,
when the concentration ratio of Bi contained in the solder plating layer is expressed as follows, the concentration ratio is in the range of 91.4 to 106.7%.
Measured value (% by mass) of Bi/target Bi content (% by mass)
Or,
concentration ratio (%) -% of the average value (mass%) of measured values of Bi/target Bi content (% by mass)
The core material of the present invention as set forth in item 2 is characterized in that the core material has a plating solder plating layer of a (Sn-58Bi) solder alloy containing Sn and 58 mass% Bi, the plating solder alloy being formed by plating solder on the core surface,
the core is formed of a single metal of Cu, Ni, Ag, Bi, Pb, Al, Sn, Fe, Zn, In, Ge, Sb, Co, Mn, Au, Si, Pt, Cr, La, Mo, Nb, Pd, Ti, Zr, Mg, or an alloy, a metal oxide, or a mixed metal oxide of two or more of these metals,
when the concentration ratio of Bi contained in the solder plating layer is expressed as follows, the concentration ratio is in the range of 91.4 to 108.6%.
Measured value (% by mass) of Bi/target Bi content (% by mass)
Or,
concentration ratio (%) -% of the average value (mass%) of measured values of Bi/target Bi content (% by mass)
Here, (Sn-58Bi) is (Sn-58 wt% Bi).
The core material of the present invention as set forth in item 3 has a plating solder plating layer of a (Sn-40Bi) solder alloy containing Sn and 40 mass% Bi, the plating solder plating layer being formed by plating solder on the core surface,
the core is formed of a single metal of Cu, Ni, Ag, Bi, Pb, Al, Sn, Fe, Zn, In, Ge, Sb, Co, Mn, Au, Si, Pt, Cr, La, Mo, Nb, Pd, Ti, Zr, Mg, or an alloy, a metal oxide, or a mixed metal oxide of two or more of these metals,
when the concentration ratio of Bi contained in the solder plating layer is expressed as follows, the concentration ratio is in the range of 90 to 107.5%.
Measured value (% by mass) of Bi/target Bi content (% by mass)
Or,
concentration ratio (%) -% of the average value (mass%) of measured values of Bi/target Bi content (% by mass)
Here, (Sn-40Bi) is (Sn-40 wt% Bi).
The core material of the present invention as set forth in item 4 is characterized in that the core material has a plating solder plating layer of a (Sn-3Bi) solder alloy containing Sn and 3 mass% Bi, the plating solder alloy being formed by plating solder on the core surface,
the core is formed of a single metal of Cu, Ni, Ag, Bi, Pb, Al, Sn, Fe, Zn, In, Ge, Sb, Co, Mn, Au, Si, Pt, Cr, La, Mo, Nb, Pd, Ti, Zr, Mg, or an alloy, a metal oxide, or a mixed metal oxide of two or more of these metals,
when the concentration ratio of Bi contained in the solder plating layer is shown below, the concentration ratio is in the range of 90 to 106.7%.
Measured value (% by mass) of Bi/target Bi content (% by mass)
Or,
concentration ratio (%) -% of the average value (mass%) of measured values of Bi/target Bi content (% by mass)
Here, (Sn-3Bi) is (Sn-3 wt% Bi).
The core material of the present invention according to claim 5 is the core material according to any one of claims 1 to 4, wherein the core material is characterized by having a base plating layer of 1 or more elements selected from Ni and Co and the plating solder plating layer in this order from the core surface.
The core material of the present invention described in item 6 is the core material described in any one of items 1 to 5, wherein Cu balls are used as the core.
The core material of the present invention described in item 7 is the core material described in any one of items 1 to 5, characterized in that a Cu pillar is used as the core.
The semiconductor package according to the present invention as set forth in item 8 is a semiconductor package using the core material as set forth in any one of items 1 to 7.
The method for forming a bump electrode according to the present invention as set forth in claim 9 is characterized by comprising:
a step of mounting a core material on the electrode; and
a step of heating the mounted core material to form a bump electrode,
the core material has an electroplated solder coating layer of (Sn-Bi) solder alloy containing Sn and Bi formed by electroplating solder on the surface of the core,
the core is formed of a single metal of Cu, Ni, Ag, Bi, Pb, Al, Sn, Fe, Zn, In, Ge, Sb, Co, Mn, Au, Si, Pt, Cr, La, Mo, Nb, Pd, Ti, Zr, Mg, or an alloy, a metal oxide, or a mixed metal oxide of two or more of these metals,
when the concentration ratio of Bi contained in the solder plating layer is expressed as follows, the concentration ratio is in the range of 91.4 to 106.7%.
Measured value (% by mass) of Bi/target Bi content (% by mass)
Or,
concentration ratio (%) -% of the average value (mass%) of measured values of Bi/target Bi content (% by mass)
Bi in the solder plating layer is treated so that its concentration distribution is uniform over the entire region from the inner peripheral side toward the outer peripheral side with respect to the plating thickness (in the case where a base plating layer such as Ni plating is applied to the core, the base plating layer is not included).
The Sn-based solder alloy may contain other additive elements in addition to the (Sn-Bi) -based solder alloy. The element that can be added to the (Sn-Bi) solder alloy includes one or more elements selected from Ag, Cu, Ni, Ge, Ga, In, Zn, Fe, Pb, Sb, Au, Pd, and Co. For example, a (Sn-Bi-Cu-Ni) solder alloy, a (Sn-Ag-Cu-Bi) solder alloy, and the like are conceivable.
The core material is obtained by forming a plating film on the surface of a core by plating a solder alloy of (Sn-Bi) system containing Sn and Bi, wherein the Bi in the solder plating layer is distributed in the solder plating layer in a concentration ratio of a predetermined range, and the Bi in the solder plating layer is distributed in a predetermined range of 91.4-106.7%. The concentration ratio (%) will be described later.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the core material of the present invention, since Bi in the plating solder plating layer is uniform, the Bi concentration ratio is within a predetermined range over the entire region including the inner peripheral side and the outer peripheral side of Bi with respect to the film thickness of the solder plating layer. Therefore, the following does not occur: the inner periphery side melts earlier than the outer periphery side, and a volume expansion difference is generated between the inner periphery side and the outer periphery side, so that the core material is flicked.
Further, since Bi in the electroplated solder plating layer is uniform, Bi is melted substantially uniformly over the entire surface of the core material, and therefore, a time difference hardly occurs in the timing of melting in the solder plating layer. As a result, positional displacement of the core material due to variation in melting timing does not occur, and thus there is no fear of short-circuiting between electrodes or the like due to positional displacement or the like. Therefore, by using the core material, a high-quality semiconductor package can be provided. In the present invention, in order to solve the problem of the plating solder having a non-uniform concentration although the film thickness can be uniformly controlled, the core material having a uniform plating layer of the plating solder can be obtained by controlling the Bi concentration ratio within a predetermined range.
Drawings
Fig. 1 is a sectional view showing an example of the structure of a Cu core ball according to an embodiment of the present invention.
Fig. 2 is a sectional view showing an example of the structure of a Cu core ball according to another embodiment of the present invention.
FIG. 3 is an enlarged sectional view showing an example of the structure of a Cu core ball showing the Bi distribution state in a solder plating layer.
Fig. 4 is a further enlarged cross-sectional view of fig. 3.
Fig. 5 is a sectional view (FE-EPMA) photograph of a main portion showing the distribution state of Sn and Bi in an enlarged manner.
FIG. 6 is a characteristic curve of the relationship between the Bi concentration in the plating solution and the Bi concentration in the solder plating layer in the plating treatment in example 1, with the Cu core ball diameter as a reference.
Fig. 7 is an explanatory view showing an example of a method of measuring the Bi concentration distribution of the core material.
FIG. 8 is a characteristic diagram of the relationship between the Bi concentration in the plating solution and the Bi concentration in the solder plating layer in the plating treatment in example 2, with the Cu core ball diameter as a reference.
Description of the reference numerals
10 Cu core ball
12 Cu ball
14 base plating layer
16 soft solder plating layer
16a inner layer
16b intermediate layer
16c outer layer
17a to 17c slice (measurement area)
Detailed Description
Example 1
Hereinafter, preferred embodiments of the present invention will be described in detail.
The present invention provides a core material obtained by forming a plating film on a core surface of a Sn-based solder alloy containing Sn and Bi by plating, wherein the distribution of Bi in the solder plating layer is uniform, and a semiconductor package using the same.
The composition of the solder plating layer of the present invention includes a (Sn-Bi) alloy containing Sn and Bi. When the Bi content is in the range of 0.1 to 99.9 mass% based on the Bi content of the entire alloy, the Bi concentration ratio can be controlled within a predetermined range of 91.4 to 106.7%, and the Bi distribution in the solder plating layer can be made uniform.
For example, in the case of a (Sn-58Bi) solder alloy, the distribution of Bi as a target value is 52 mass% (concentration ratio 91.4%) to 63 mass% (concentration ratio 108.6%) with 58 mass% as a target value and within an allowable range.
The allowable range means a range within which soldering such as bump formation can be performed without any problem. The concentration ratio (%) refers to a ratio of a measured value (% by mass) to a target content (% by mass) or a ratio of an average value (% by mass) of the measured values to the target content (% by mass). That is, the concentration ratio (%) can be expressed as follows.
Concentration ratio (%) — measured value (% by mass)/target content (% by mass)
Or,
concentration ratio (%) — average value (mass%) of measured values/content (mass%) of target
Even if an additional element is added to a binary electroplating solder plating layer containing Sn and Bi, the Bi concentration ratio can be controlled within a predetermined range of 91.4 to 106.7%.
As the additive element, one or two or more kinds of Ag, Cu, Ni, Ge, Ga, In, Zn, Fe, Pb, Sb, Au, Pd, Co, and the like can be considered.
As the core (core), a metal material is used. The shape of the core may be a sphere or the like (columnar column, sheet, etc.). In this example, a case of using a Cu core ball as a core, particularly, a ball made of Cu (hereinafter referred to as a Cu ball) will be described.
The particle diameter (ball diameter) of the Cu ball also varies depending on the size of the BGA, and in the following example, it is assumed thatLeft and right spherical shape, thickness of one side of solder plating layer in radial direction20 to 100 μm. The particle diameter of the Cu core ball is appropriately selected according to the density and size of the electronic component to be used, and the Cu ball may be used in a range of 1 to 1000 μm, and the plating thickness is appropriately selected according to the particle diameter of the Cu ball to be used. The plating apparatus for performing the plating treatment uses an electroplating apparatus.
Next, an example of a Cu core ball using a Cu ball is shown.
Fig. 1 is a cross-sectional view showing an example of a Cu core ball 10 of the present invention. The illustration is exaggerated for the sake of convenience of explanation.
Cu core ball 10 is formed with Cu ball 12 and solder plating layer 16 made of Sn-based solder alloy with Ni base plating layer 14 interposed therebetween in this example. The Ni base plating layer 14 functions as a base plating layer for preventing a change in the composition of the solder plating layer 16 due to metal diffusion between the Cu ball 12 and the solder plating layer 16, and has a thickness of about 1 to 4 μm. The Ni base plating layer 14 is not necessarily required to have a composition, and a solder plating layer may be directly formed on the surface of the Cu ball 12 as shown in fig. 2. When the base plating layer 14 is formed, the base plating layer 14 may be formed of a layer containing 1 or more elements selected from Ni and Co.
The Cu used for the Cu balls 12 may be pure copper or an alloy of copper.
When the Cu balls 12 composed of an alloy containing Cu as a main component are used, the purity is not particularly limited, and is preferably 99.9 mass% or more from the viewpoint of suppressing deterioration of the electrical conductivity and the thermal conductivity of the Cu core ball due to a decrease in the purity and, if necessary, suppressing α -ray dose.
The core may be composed of a single metal, or an alloy, a metal oxide, or a mixed metal oxide of two or more metals selected from Ni, Ag, Bi, Pb, Al, Sn, Fe, Zn, In, Ge, Sb, Co, Mn, Au, Si, Pt, Cr, La, Mo, Nb, Pd, Ti, Zr, and Mg, In addition to Cu.
From the viewpoint of controlling the height of the nugget, the sphericity of the Cu ball 12 is preferably 0.95 or more, and more preferably 0.990 or more. When the sphericity of the Cu balls 12 is less than 0.95, the Cu balls 12 have irregular shapes, and therefore, bumps having uneven heights are formed during bump formation, and the possibility of occurrence of poor bonding is high. Further, when the Cu core ball 10 is mounted on an electrode and reflow-soldered, if the sphericity is low, the Cu core ball 10 is displaced, and self-alignment is also deteriorated.
Here, the sphericity degree represents a deviation from a perfect sphere. The sphericity can be determined by various methods such as a least squares center method (LSC method), a minimum area center method (MZC method), a maximum inner center method (MIC method), and a minimum outer center method (MCC method). Specifically, the sphericity is an arithmetic average value calculated by dividing the diameter of each of 500 Cu balls by the major axis, and indicates that the value is closer to 1.00 as the upper limit, which is closer to a perfect sphere. The long diameter length is measured by an Ultra Quick Vision manufactured by Mitutoyo corporation, ULTRA QV350-PRO measuring apparatus.
The diameter of the entire Cu core ball 10 including the solder plating layer 16 is preferably 1 to 1000 μm. Within this range, the spherical Cu core ball 10 can be stably produced, and the particle diameter is selected to suppress a short circuit in connection when the electrode terminals have a narrow pitch.
An aggregate of the Cu core balls 10 having a particle diameter of about 1 to 300 μm is sometimes referred to as "Cu core powder". The Cu core powder may be used in a state of being mixed with solder as a powder in a solder paste.
The solder plating layer 16 is a solder alloy, and in this example, contains Sn and Bi.
In this case, as described above, the Bi content in the solder plating layer 16 is preferably about 53 mass% (concentration ratio 91.4%) to 63 mass% (concentration ratio 108.6%) as an allowable range with respect to 58 mass% of the target value.
The thickness of the solder plating layer 16 varies depending on the particle size of the Cu ball 12, and is preferably 100 μm or less on one side in the radial direction. For example, as particle sizeThe Cu ball 12 of (2) is formed with a solder plating layer 16 having a thickness of 50 to 70 μm. This is to ensure a sufficient solder bonding amount.
As the plating solution, a mixed solution of an organic acid, Bi methanesulfonic acid, and a surfactant is used. The concentration of the plating solution is controlled in a constant manner in the formation of the solder plating layer.
When a solder plating layer made of an Sn — Bi solder alloy containing Sn and Bi is formed by electroplating, Bi is introduced into the solder plating layer more preferentially than Sn, and therefore there is a problem that the Bi concentration in the plating solution does not match the Bi amount in the solder plating layer, and a solder alloy plating layer having a uniform Bi concentration distribution cannot be formed. Therefore, the plating treatment was performed under the conditions shown in fig. 6 by applying a predetermined dc voltage between the anode and the cathode and by shaking the Cu ball to adjust the Bi concentration in the liquid uniformly.
The process of producing the solder plated layer 16 by this plating process will be described in further detail with reference to fig. 6. Fig. 6 is a characteristic graph of the relationship between the Bi concentration in the plating solution (curve Lb) and the Bi concentration in the solder plating layer 16 (curve La) in the plating process with the Cu core ball diameter as a reference.
In this example, Cu balls having a particle size of 215 μm were used as the initial values of the Cu balls. The thickness of the solder plating layer 16 was monitored one by one, and in this example, the Cu core ball 10 was sampled every time the thickness of the solder plating layer 16 was increased by a predetermined value. The collected sample was dried after washing, and then the particle size was measured.
When the Bi content in the solder plating layer was measured in order when the grain size of the Cu core ball at the measurement timing became the target value, the results shown by the curve La in fig. 6 were obtained. From the results, it is understood that even if the solder plating layer 16 is increased in a predetermined thickness in this order, the Bi content at this time is substantially the same as the above content. In the case of the curve La, the Bi content is substantially 58 to 60 mass%. Therefore, as can be understood from the curve La in fig. 6, the concentration distribution of Bi is uniform (equal) with respect to the thickness of the plating layer, and there is no concentration gradient.
Fig. 3 shows a cross-sectional view of the Cu core ball 10 at this time. From fig. 4 enlarged and fig. 5 further enlarged, it is clear that Sn and Bi are uniformly mixed and grown in solder plating layer 16. Fig. 5 is photographed using FE-EPMA.
Since the concentration of Bi in the solder plating layer 16 is maintained in almost the same state even if the thickness of the solder plating layer 16 grows, it is clear that Bi in the solder plating layer 16 grows (precipitates) in a state in which Bi is distributed almost uniformly. The plating treatment is performed in a state where the Bi concentration in the plating solution is uniform so that the Bi concentration is within a desired value. In this example, since the content of Bi in the solder plating layer 16 is set to a target value of 58 mass%, the Bi concentration in the plating solution is controlled so as to reach the target value.
In order to set the concentration distribution of Bi in the solder plating layer 16 to a desired value, the plating treatment is performed while performing voltage/current control. By this plating treatment, the distribution of Bi in the solder plating layer 16 can be maintained at a desired value.
In the examples, the Bi concentration in the plating solution was approximately 42 to 44 mass% in the plating treatment because the plating treatment was performed while adjusting the Bi concentration in the plating solution as needed so that the Bi concentration in the solder plating layer 16 was 53 to 63 mass%, as described above.
The reason why the Bi concentration in the solder plating layer 16 shown by the curve La does not match the Bi concentration in the plating solution shown by the curve Lb is that Bi in the plating solution is introduced into the solder plating layer more preferentially than Sn in the plating solution.
In order to confirm that the concentration distribution of Bi in solder plating layer 16 is a value corresponding to the target value, the following experiment was performed.
(1) A Cu core ball 10 having a composition of (Sn-58) Bi of solder plating layer 16 was produced under the following conditions.
Diameter of Cu ball 12: 250 μm
Film thickness of the Ni base plating layer 14: 2 μm
Film thickness of solder plating layer 16: 23 μm
Diameter of Cu core ball 10: 300 μm
In order to easily measure the experimental results, a Cu core ball having a solder plating layer with a small thickness was produced as the Cu core ball 10.
The plating method is fabricated by an electroplating process under the conditions of fig. 6.
(2) As samples, 10 Cu core balls 10 each having a solder plating layer of (Sn-58Bi) based solder alloy of the same composition were prepared. They were used as sample A.
(3) Each of the samples A1 to A10 was sealed with a resin.
(4) The sealed samples a1 to a10 were polished together with a resin, and the cross sections of the samples a1 to a10 were observed. The observation device used was FE-EPMAJXA-8530F manufactured by Japan electronic Co.
Fig. 7 shows a cross-sectional view of sample a 1. For convenience, the solder plating layer 16 is divided into an inner layer 16a, an intermediate layer 16b, and an outer layer 16c from the surface side of the Cu ball 12. In this example, as shown in fig. 7, regions 17a, 17b, and 17c having a width of 40 μm are cut out at a thickness of 5 μm from the inner layer 16a to 9 μm, the intermediate layer 16b to 9 μm, and the outer layer 16c to 17 to 23 μm from the surface of the Cu ball 12, and the thickness of the regions 17a, 17b, and 17c is measured by qualitative analysis. This operation is performed for each of the inner layer 16a, the intermediate layer 16b, and the outer layer 16c one by one in a total of 10 fields of view.
The results are summarized in (Table-1). From this (Table-1), it was found that the minimum value of the concentration was in the range of 53.29 mass% (concentration ratio of 91.9%) and the maximum value of the concentration was in the range of 60.97 mass% (concentration ratio of 105.1%) in the inner layer, the intermediate layer and the outer layer. As described above, the allowable range of Bi is set to 53 mass% (concentration ratio 91.4%) to 63 mass% (concentration ratio 108.6%), but the range of 53.29 mass% (concentration ratio 91.9%) to 60.97 mass% (concentration ratio 105.1%) can be allowed based on the actual measurement value of the experimental result.
[ TABLE 1]
Further, the arithmetic mean of samples a1 to a10 was calculated, and the result was:
the inner layer region 17a is 57.46 (mass%) (concentration ratio 99.1%)
The intermediate layer region 17b was 56.32 (mass%) (concentration ratio 97.1%)
The outer layer region 17c was 56.62 (mass%) (concentration ratio 97.6%).
It is also understood that when the regions 17a to 17c of the inner layer, the intermediate layer, and the outer layer are arithmetically averaged as described above, Bi in the solder plating layer falls within the above allowable range of 53 mass% to 63 mass%, and therefore, the Bi concentration ratio is substantially the target value.
The measurement operations were similarly performed for samples B to D prepared separately from sample a, and the results are shown in table-2.
[ TABLE 2 ]
From the results (Table-2), it was found that the Bi concentration in the solder plating layer 16 was 53 to 63 mass% of the target value, although the Bi concentration was somewhat fluctuated.
Further, 10 (examples) of Cu core balls produced in the same batch as those of samples a to D were extracted and bonded to a substrate by a normal reflow process.
The results of the bonding are also shown in Table-2.
As for the bonding results, the case where no bonding failure was measured in all the samples was judged as "good", and the case where the positional deviation occurred in the bonding of 1 sample and the case where the Cu core ball 10 was popped off in the bonding of 1 sample were judged as "poor".
There is no case where the Cu core ball 10 is flicked off due to the inner periphery melting earlier than the outer periphery and the difference in volume expansion between the inner periphery and the outer periphery, and the solder plating layer 16 is substantially uniformly melted as a whole, and therefore, there is no positional deviation of the core material which is considered to occur due to the variation in melting timing, and there is no fear of short circuit between electrodes or the like due to the positional deviation or the like. Therefore, a good result was obtained in which no defective bonding occurred at all, and the result was judged to be "good".
Example 2
The second embodiment is an example of forming the solder plating layer 16 of a quaternary Sn-based solder alloy composed of (Sn-Cu-Bi-Ni) containing Cu and Ni in addition to Sn and Bi. The target value is, for example, the following composition.
Bi: 40 mass%, Cu: 0.5 mass%, Ni: 0.03 mass%, Sn: and (4) the balance. The target value of the Bi distribution at this time was 40 mass%, and the allowable range was 36 mass% (concentration value 90%) to 43 mass% (concentration ratio 107.5%).
Specifically, a Cu core ball having a composition of a solder plating layer expressed as (Sn-40Bi-0.5Cu-0.03Ni) as described above was produced under the following conditions.
Diameter of Cu ball: 180 μm
Film thickness of Ni base plating layer: 2 μm
Film thickness of solder plating layer: 33 μm
Diameter of Cu core ball: 250 μm
The Cu core ball was produced under the same plating conditions as in example 1 so that the Bi concentration in the plating solution was uniform.
The experimental method was carried out under the same conditions as in example 1 except that the inner layer 16a was set to 11 μm from the surface of the Cu ball, the intermediate layer 16b was set to 11 to 22 μm, and the outer layer 16c was set to 22 to 33 μm.
The results of the measurement are shown in E to H in Table-2.
From the results of samples E to H (table-2), it is understood that the target value of Bi at this time is 40 mass%, and the average value of Bi in the solder plating layer 16 at this time is from 37.81 mass% minimum (concentration ratio 94.5%) to 41.33 mass% maximum (concentration ratio 103.3%) (all average values obtained by measuring 10 times for solder alloys of the same composition), and there are some variations, but it is within 36 mass% (concentration ratio 90.0%) to 43 mass% (concentration ratio 107.5%) approximately corresponding to the target value, that is, within the allowable range). In all the samples, the joining judgment obtained a good result that no joining failure occurred at all, as in example 1, and was therefore judged to be "good".
Fig. 8 is a characteristic diagram of the relationship between the Bi concentration in the plating solution (curve Lc) and the Bi concentration in the solder plating layer 16 (curve Ld) in the electroplating process based on the Cu core ball diameter, similarly to fig. 6.
In this example, as in example 1, Cu balls having a particle size of 215 μm were used as the initial values of the Cu balls. The thickness of the solder plating layer 16 was monitored one by one, and in this example, the Cu core ball 10 was sampled every time the thickness of the solder plating layer 16 was increased by a predetermined value. The collected sample was dried after washing, and then the particle size was measured.
When the content of Bi in the solder plating layer was measured in order when the grain size of the Cu core ball at the measurement timing became the target value, the result as shown by the curve Lc in fig. 8 was obtained. From the results, it is understood that even if the solder plating layer 16 is increased in a predetermined thickness in this order, the Bi content at this time is substantially the same as the above content. In the case of the curve Lc, the Bi content is approximately 40 to 42 mass%. Therefore, as can be understood from the curve Lc, the concentration distribution of Bi is uniform (uniform) with respect to the plating thickness, and there is no concentration gradient. The reason why the Bi concentration in the solder plating layer 16 (curve Lc) is not equal to the Bi concentration in the plating solution (curve Ld) is that, as in fig. 6, Bi in the plating solution is introduced into the solder plating layer more preferentially than Sn in the plating solution.
Example 3
In example 3, the same measurement was performed for the case of forming the solder plating layer 16 of a quaternary Sn-based solder alloy composed of (Sn-3Ag-0.8Cu-3Bi) containing Ag and a small amount of Bi. The target value of the Bi distribution at this time was 3 mass%, and the allowable range was 2.7 mass% (concentration value: 90.0%) to 3.2 mass% (concentration value: 106.7%).
The Cu core ball was produced in the same manner as in examples 1 and 2.
Specifications and experimental conditions such as the diameters of the Cu balls and Cu core balls used, and the film thicknesses of the Ni base plating layer and the solder plating layer were the same as those in example 1 except for the composition of the solder plating layer.
The results are shown in (Table-2) for samples I to L. In this case, since Bi as the target value is 3 mass%, as shown in samples I to L, the target value is about 2.81 to 3.08 mass% (each average value measured 10 times for the same sample) and has some variation (the minimum 2.81 mass% (concentration ratio 93.7%) to the maximum 3.08 mass% (concentration ratio 102.7%) of the average value, but is within the allowable range, it is found that the target value is 2.7 mass% (concentration ratio 90.0%) to 3.2 mass% (concentration ratio 106.7%), and the judgment of bonding is "good" because a good result that no bonding failure occurs at all is obtained as in example 1.
The results of [ example 1] to [ example 3] are shown in Table-3. The Bi concentration ratio is 91.4 to 106.7% by mass.
[ TABLE 3]
The experimental results of the conventionally known solder plating layer in which the distribution of Bi has a concentration gradient are shown in the above (table-2) as comparative examples. The conditions of the Cu balls used, the ball diameters of the Cu core balls, the film thicknesses of the Ni base plating layer and the solder plating layer, and the like, and the experimental conditions were the same as those of example 1 except for the following plating method.
Comparative example 1
In comparative example 1, the plating solution was plated with a plating solution containing Sn methanesulfonate, an organic acid, and a surfactant. Further, only the methanesulfonic acid Bi was added at a stage when the plating film thickness was half the target value. Thus, the plating treatment was performed while decreasing the concentration of Sn methanesulfonate and increasing the concentration of Bi methanesulfonate in the plating solution.
As a result, a solder plating layer was formed having a concentration gradient (inner layer 0 mass%, middle layer 52.12 mass%, outer layer 100 mass%) in which the Bi concentration in the solder plating layer was low on the inner side and gradually increased toward the outer side, so that the Bi content as the entire solder plating layer became the target value of 58 mass%.
Comparative example 2
In comparative example 2, electroplating was performed using a plating solution containing Sn methanesulfonate, Bi methanesulfonate, an organic acid, and a surfactant. After the start of plating, a predetermined direct current voltage is applied between the anode and the cathode, and the plating process is performed while shaking the Cu balls.
As a result, a solder plating layer was formed which exhibited a concentration gradient (inner layer 70.7 mass%, middle layer 24.8 mass%, and outer layer 3.8 mass%) in which the Bi concentration in the solder plating layer was high on the inner side and gradually decreased toward the outer side, and the Bi content as the entire solder plating layer was set to a target value of 58 mass%.
As a result, comparative example 1 was determined to be "defective" because the position was shifted during bonding, and comparative example 2 was determined to have Cu core balls popped off.
When the Bi concentration in solder plating layer 16 is changed in this way, displacement, blow-off of Cu core ball 10, and the like occur.
In the present invention, Bi contained in the material having the core surface covered with the solder plating layer is uniform. For example, the core material of the present invention can be used as a solder bump in a semiconductor package such as BGA. As the core, a ball is suitable, and a metal ball such as Cu is suitable.
The scope of the present invention is not limited to the above embodiments, and various modifications may be made to the above embodiments without departing from the spirit of the present invention. The shape also includes a spherical shape (columnar column, sheet, etc.).
For example, the diameters of the upper and bottom surfaces: 1-1000 μm, height: in a Cu stem obtained by providing a Ni base plating layer, an Fe base plating layer, a Co base plating layer, etc. of 1 to 4 μm on one side on the surface of a1 to 3000 μm Cu stem and covering the (Sn-Bi) solder plating layer under the same conditions as in examples, Bi in the solder plating layer has a concentration ratio in a predetermined range of 91.4 to 106.7%, and as in the case of the Cu core ball of the examples of the present application, no bonding failure occurs.
Industrial applicability
The core material of the present invention can be used as a bonding material for a semiconductor package such as BGA.

Claims (11)

1. A core material having an electroplated solder coating layer of an Sn-Bi solder alloy containing Sn and Bi, which is formed by electroplating solder on a core surface,
the core is formed by metal simple substances of Cu, Ni, Ag, Bi, Pb, Al, Sn, Fe, Zn, In, Ge, Sb, Co, Mn, Au, Si, Pt, Cr, La, Mo, Nb, Pd, Ti, Zr and Mg or alloy, metal oxide or metal mixed oxide of more than two of the metal simple substances,
when the concentration ratio of Bi contained in the solder plating layer is represented as follows, the concentration ratio is in the range of 91.4 to 106.7%,
measured value (% by mass) of Bi/target Bi content (% by mass)
Or,
concentration ratio (%) -% of the average value (mass%) of measured values of Bi/target Bi content (mass%).
2. A core material having an electroplated solder coating layer of an Sn-58Bi solder alloy containing Sn and 58 mass% Bi, the electroplated solder coating layer being formed by electroplating solder on a core surface,
the core is formed by metal simple substances of Cu, Ni, Ag, Bi, Pb, Al, Sn, Fe, Zn, In, Ge, Sb, Co, Mn, Au, Si, Pt, Cr, La, Mo, Nb, Pd, Ti, Zr and Mg or alloy, metal oxide or metal mixed oxide of more than two of the metal simple substances,
when the concentration ratio of Bi contained in the solder plating layer is represented as follows, the concentration ratio is in the range of 91.4 to 108.6%,
measured value (% by mass) of Bi/target Bi content (% by mass)
Or,
concentration ratio (%) -% of the average value (mass%) of measured values of Bi/target Bi content (mass%).
3. A core material having an electroplated solder coating layer of an Sn-40Bi solder alloy containing Sn and 40 mass% Bi, the electroplated solder coating layer being formed by electroplating solder on a core surface,
the core is formed by metal simple substances of Cu, Ni, Ag, Bi, Pb, Al, Sn, Fe, Zn, In, Ge, Sb, Co, Mn, Au, Si, Pt, Cr, La, Mo, Nb, Pd, Ti, Zr and Mg or alloy, metal oxide or metal mixed oxide of more than two of the metal simple substances,
when the concentration ratio of Bi contained in the solder plating layer is expressed as follows, the concentration ratio is in the range of 90 to 107.5%,
measured value (% by mass) of Bi/target Bi content (% by mass)
Or,
concentration ratio (%) -% of the average value (mass%) of measured values of Bi/target Bi content (mass%).
4. A core material having an electroplated solder coating layer made of an Sn-3Bi solder alloy containing Sn and 3 mass% Bi, the electroplated solder coating layer being formed by electroplating a solder on a core surface,
the core is formed by metal simple substances of Cu, Ni, Ag, Bi, Pb, Al, Sn, Fe, Zn, In, Ge, Sb, Co, Mn, Au, Si, Pt, Cr, La, Mo, Nb, Pd, Ti, Zr and Mg or alloy, metal oxide or metal mixed oxide of more than two of the metal simple substances,
when the concentration ratio of Bi contained in the solder plating layer is expressed as follows, the concentration ratio is in the range of 90 to 106.7%,
measured value (% by mass) of Bi/target Bi content (% by mass)
Or,
concentration ratio (%) -% of the average value (mass%) of measured values of Bi/target Bi content (mass%).
5. The core material according to any one of claims 1 to 4, characterized in that the core material has a base plating layer of 1 or more elements selected from Ni and Co and the electroplating solder plating layer in this order from the core surface.
6. The core material according to any one of claims 1 to 4, wherein Cu balls are used as the core.
7. The core material according to claim 5, characterized in that Cu spheres are used as core.
8. The core material according to any one of claims 1 to 4, wherein Cu pillars are used as the core.
9. The core material according to claim 5, characterized in that Cu columns are used as core.
10. A semiconductor package characterized by using the core material according to any one of claims 1 to 9 as a solder bump.
11. A method for forming a bump electrode, comprising:
a step of mounting a core material on the electrode; and
a step of heating the mounted core material to form a bump electrode,
the core material has a plating solder coating layer of Sn-Bi solder alloy containing Sn and Bi formed by plating solder on the surface of the core,
the core is formed by metal simple substances of Cu, Ni, Ag, Bi, Pb, Al, Sn, Fe, Zn, In, Ge, Sb, Co, Mn, Au, Si, Pt, Cr, La, Mo, Nb, Pd, Ti, Zr and Mg or alloy, metal oxide or metal mixed oxide of more than two of the metal simple substances,
when the concentration ratio of Bi contained in the solder plating layer is represented as follows, the concentration ratio is in the range of 91.4 to 106.7%,
measured value (% by mass) of Bi/target Bi content (% by mass)
Or,
concentration ratio (%) -% of the average value (mass%) of measured values of Bi/target Bi content (mass%).
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